Process of preparing 4-methyl-7-bis (beta-hydroxyethyl) amino coumarin



Patented June 8, 1954 PROCESS OF PREPARING 4-METHYL-7-;

BIS (BETA HYDROXYETHYL)AMINO COUMARIN William Wilson Williams and Harlan Benjamin Freyermuth, Easton, Pa.,

assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application May 19, 1951, Serial No. 227,282

This invention relates to novel 7-hydroxyalkylamino 4 substituted coumarin compounds which have been found to be of value as fluorescent brightening or whitening agents.

1 Claim. (c1. zoo-343.2)

. 2 manner described in U. S. Patent 1,712,716 for the preparation of 4(bis)hydroxyethylaminophenol from 4-aminophenol. The 3-diethanolamino phenol is then reacted with ethyl acetoacetate in These novel compounds may be prepared by 5 the following manner, an excess of ethyl aceto condensing N-hydroxyalkyl 3-aminopheno1s with acetate preferably being used so that about 1.1 to a fl-keto ester in alcoholic solution and in the 1.3 molar parts of ethyl acetoacetate are present presence of zinc chloride. The novel compounds for each molar part of 3-diethanolaminophenol. of the present invention may be represented by Amixture of 87 parts of B-diethanolaminophenol, the following formula: 93 parts ethyl acetoacetate, 35 parts zinc chloride and 160 parts ethanol was refluxed for ten hours The ethanol and excess ethyl acetoacetate were l then removed by steam distillation and the hot aqueous solution of the product decolorized by C 5 treatment with animal charcoal and filtered.

| Upon cooling, the product crystallized from the X solution and was purified by recrystallization from hot water. If desired, other conventional wherein R hydroxyalkyl group purification methods may be employed such as -CH2CH2OH, -CH2CI-IOHCH3 dissolving the product in a, solution of hydroand CHZCOH(CI I3)2) R2 is hydrogen alkyl or chlorcilc acid nd rieprecipitating with a solution i 0 so ium car ona e.

the same as X 15 hydrogen CH3, CF3' The thus obtained product, 7-diethanolamino; C6H5 COOH' TCOOCHs, BQ 4-methylcoumarin, was applied to wool from acid, gkclliigoiocintl arlld Y is hlyidrogen 25 neutral and alkaline baths and found to produce y y roxya ky and fina y X and Y oge er a substantial whitening effect. The product was may the group CH2 CH2CH2 C-H2' mixed with ordinary soap flakes and employed for The p1 Oducts of the above formula h 'i the washing of wool and found to exert a consid- 22223 2 3 25 jfi g f fi ggfigg z gggg ggfi% erable whitening effect under these conditions. lose acetate, etc. and have been found to be of It s also apphEidTfmm i i g particular value for the whitening of proteinaaceta rayon ny OP and S1 and mm o ceous fibers such as wool and silk or nitrogenous gi gig l ggigfg i gg iii ggg i fibers such as nylon from acid, alkaline or neutral methgd forgpregparmg the novel compounds of baths' f h this invention, and while the 7-diethanolamino minorvamount'of the product in soap orjother fluorescent agent of the present invention, it W111 g t nt 0m 10 ed for Washing the matezgial to be understood that other related 7-alky1olammob: iri i tened 'I hese novel products have also 'substituted coumairins. of the type included in been found to be useful as fluorescent brightening 4.0 the general m glven w l agents where spirit solubility is desired, such for pronounced whltenlmg 0r br ghtening action. example in the whitening of nitrocellulose lacsuch other f readlly Prepared quers, whitening of beeswax and other natural I the manner descrlbfled 1n the fOIegPmg and synthetic waxes and the whitening of natural by p yi other f l yl l ammoph l 1n and synthetic resins. place of the 3-diethanolam1nophenol used in the The details of the preparation of these novel f re in example and by mplo mg th B-k to compounds will be apparent from the following esters in p ace of the ethyl c o y d specific example in which the parts are by Weight: in t e f e o g mp a-diethanolaminophenol was prepared by re- A number of specific-productscomingwithin acting B aminophenol with ethylene oxide in the the present invention and the 3 alkylolaminophe? Table-Continued 3 alkylolamino phenol used fl-keto ester used Product I HO-CHa-CE: HzCOCHaCOOC2H5 HOCHPOEi 0 N- CH ethylacetoaeetate /N HaC-H2C H=o-mo 5 3-(2 ethylamlnoethanol) -phenol (3H3 7(2-ethyIamino-ethanol) -4-methyl coumarin We claim:

coumarin.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,600,375 Ackerman June 14, 1946 2,610,152 Ackerman Sept. 9, 1952 OTHER REFERENCES Von Pechmann et a1., Beilstein (Handbuch, 4th ed), v01. 18, page 610 (1934). 

